Synthesis and electro-optic activities of new side-chain polycarbonates containing nonlinear optical chromophores and isolation groups

Abstract

Dendritic julolidine-based nonlinear optical (NLO) chromophore (JTCFC) possessing isolation group was designed and synthesized to realize effective isolation of NLO chromophores in the polymer backbone.Electro-optic (EO) polycarbonates (PC-JTCFCs) consisting of the dendritic JTCFC and comonomers were prepared through a facile copolymerization strategy. The sufficiently high polymerizability of the dendritic JTCFC, which could be caused by the well-isolation of chromophores and lack of steric effect, afforded the EO polycarbonates with ultra-high molecular weight (M w up to 145 990). The DSC analysis showed that the EO polycarbonates exhibited similar T g values (near 150 C), indicating that the interchromophore interactions are effectively suppressed. The effective isolation of NLO chromophores directly suppressed the dipole-dipole interactions and improved the translation of microscopic hyperpolarizability into macroscopic EO activity. After corona poling, the synthesized EO polycarbonates exhibited a maximum EO coefficient (r 33 ) of 55 pm V À1 at 1310 nm, which was greatly enhanced as compared to the guest-host systems reported previously. Moreover, the prepared EO polycarbonates also possessed good temporal stability, 85% of the initial r 33 value of PC-JTCFC-3 could be kept after 500 h at 85 C.

Construction of a simple crosslinking system and its influence on the poling efficiency and oriental stability of organic electro-optic materials

“…This result is much better than the sidechain polycarbonates systems we reported previously. 23 When the concentration was increased to 26 wt%, the r 33 values only changed slightly and reached the saturated value in the previous sidechain polycarbonates systems. The maximum value of polymer P3 reached 78.9 pm V À1 , and this result is much better than the doped guest-host systems (36 pm V À1 at 40 wt%) and sidechain polycarbonates systems (55 pm V À1 at 26 wt%).…”

“…In this work, the new uorinate polycarbonate P was synthesized from the monomer bisphenol AF and anthracen-9ylmethyl-4,4-bis(4-hydroxyphenyl)pentanoate with triphosgene, [21][22][23] which can afford the "D" part of the "Diels-Alder" reaction. The chromophore with the julolidinyl-based group as the electron donor and 2-dicyanomethylene-3-cyano-4-methyl-5phenyl-5-triuoromethyl-2,5-dihydrofuran (CF3-Ph-TCF) as the acceptor was also synthesized as the crosslinking agent.…”

Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure

“…Compounds presenting a pyran ring in their structures ( 232–239 ) were obtained in 23–85 % yield by using piperidine as base (Table , Entries 1–9 ) . , Julolidines 240 and 241 were produced in modest yields (44 and 55 %, respectively) using TCF as nucleophile (Table , Entries 10 and 11) , . Aldol condensation reaction using TCF as reactant in absence of base was also reported.…”

“…Aldol condensation reaction using TCF as reactant in absence of base was also reported. The conjugated julolidine 242 was obtained in 71 % yield (Table , Entry 12) …”

Organic Second-Order Nonlinear Optical Chromophores Modified by Isolation Groups

“…尽管对发色团分子结构进行修饰, 引入隔离基团是 目前最热门的研究方法, 然而一些柔性基团对于增大分 子之间的距离, 减少分子在极化过程中的堆积的效果不 是很理想, 导致微观一阶超极化率 β 值向宏观电光系数 r 33 转换的效率不高 [39] . 本课题组 [23] Figure 16 Chemical structure of the chromophore 41 [43]…”